Catalytic conversion of hydrocarbons with the stripping of the fouled catalyst particles



Jan. 17, 1956 A. BELcHETz 2,731,398

\ CATALYTIC CONVERSION OF HYDROCARBONS WITH THE STRIPPING OF THE FOULED CATALYST PARTICLES Jan. 17, 1956 A. BELcHETz 2,731,398

CATALYTIC CONVERSION OF' HYDROCARBONS WITH THE STRIPPING OF' THE FOULED CATALYST PARTICLES Original Filed Sept. 4, 1947 2 Sheets-Sheet 2 IN V EN TOR.

United States Patent O CATALYTIC CONVERSION GF HYDROCARBONS WITH THE STRIPPING F THE FOULED CATA- LYST PARTICLES Arnold Belchetz, Larchmont, N. Y., assigner to The M. W. Kellogg Co., Jersey City, N. Il., a corporation of Delaware Continuation of application Serial No. 772,170, September 4, 1947. This application May 24, 1951, Serial No. 228,010

1 Claim. (Cl. 1536-52) This case is a continuation of my co-pending application Serial No. 772,170, filed September 4, 1947, and now abandoned. The subject matter to which the claim of the present application is directed was first disclosed in my application Serial No. 274,670, now U. S. Patent 2,253,486, which was followed by a continuation-in-part application Serial No. 343,222, now abandoned, which was co-pending with the former application. Serial No. 343,222 was followed by a continuation-in-part Serial No. 559,019, now abandoned, which was co-pending with the former application. Serial No. 559,019 was followed by the above mentioned continuation application Serial No.

772,170, which was co-pending with the former appli\ cation.

In said original application, U. S. Patent No. 2,253,486, a process is disclosed for the conversion of hydrocarbons involving a continuous cyclic operation, wherein a finely divided catalytic material is mixed with a stream of the vapors of the hydrocarbons undergoing treatment, and the mixture passed continuously through a conversion zone maintained under suitable conditions to effect the desired conversion. The spent catalytic material is separated from the vaporous conversion products and regenerated for reuse in the conversion operation by combustion of the deactivating substances such as carbonaceous material deposited thereon during the conversion operation. Regeneration is then effected by mixing the spent catalytic material with an oxygen-containing gas and passing the mixture through a regeneration zone maintained under suitable conditions to effect the desired combustion without subjecting the catalyst to excessive temperatures which would unduly impair its catalytic activity.

A feature disclosed in said application Serial No. 274,670, now Patent No. 2,253,486, and to which the present application is particularly directed resides in the procedure whereby the used catalyst is separated and recovered from the eflluent conversion products from the catalytic conversion zone and returned to the regeneration zone.

In accordance with the present invention, the vaporous conversion products containing used catalyst are passed from the conversion zone to a gas-solid separating zone, or, preferably, a series of such zones, wherein all but a relatively small quantity of the catalyst is separated from the vapors, the vaporsv being maintained during the separation above the temperature at which substantial condensation can occur. In the initial separating zone, a large proportion of the used catalyst is preferable separated without any increase in the vapor velocity such as is involved in separation by means of cyclone type gassolid separators. The used catalyst is thereafter caused to ow downwardly as a layer or column in countercurrent ow with an upwardly owing stream of inert gas prior to its transfer to the regeneration zone whereby various important process advantages result, as pointed out hereinafter. The vaporous conversion products containing the small residual quantity of catalyst `are then passed to ICC a cooling zone wherein a small fraction of the highest high boiling constituents is condensed and in which heavy fraction the residual catalyst is concentrated by absorption or entrainment. The cooling and condensation step is preferably effected by passing the mixture of vapors and residual catalyst through the bottom part of a fractionating zone provided with balles over which a cooled recycled stream of the high boiling condensate is circulated and through which the vaporous mixture is passed to effect the desired separation of the catalyst by absorption or entrainment in the condensed heavy fraction.

In the appended drawings, Figure 1 is a diagrammatic illustration of a suitable form of apparatus for the practice of a preferred embodiment of the invention wherein preheated catalyst is utilized to vaporize the feed stock.

Figures 2 and 3 are enlarged and detailed views of tower 27.

Referring to the drawing, feed to the system, for example a reduced petroleum crude, enters from any convenient source indicated by the numeral 1 and pumped by pump 2 to a heater or furnace 3 wherein it is preheated to a suitable temperature then flash evaporated in evaporator 4.

The volatile portion of the crude is taken overhead from evaporator 4 as a gas oil fraction through line 5, and a heavy residual fraction is withdrawn at the bottom through line 55. From line 5 the gas oil vapors pass through a heat exchanger 6, then through a condenser coil 7 into accumulator 8. Steam vintroduced through line 9, is `condensed together with the gas oil and separated therefrom in accumulator 8 through line 10. The gas oil condensate is pumped by pump 11 through line 13 to heat exchanger 6 and into line 12. Part of the gas oil is returned as reliux to the evaporator through line 14'.

The apparatus described above is merely illustrative and exemplary of conventional apparatus for supplying the gas oil or other treated hydrocarbon at a suitable temperature for the following conversion operation.

The preheated fresh feed in transfer line 12 may be advantageously combined with a hot recycle oil containing catalyst introduced through line 14 and produced in a later stage of the process pursuant to this invention as hereinafter described. The combined feed passes through line 15 into pipe 16 constituting an extension of the conversion reactor 17. Hot preheated catalyst is supplied from a collection or surge drum 18 by suitable means such as a helical feeder 19 and mixed with the oil in pipe 16, the upper surface of the body of catalyst in drum 18 being indicated by dotted line 60. The quantity and temperature of the catalyst thus introduced preferably are sufficient to cause vaporization of the liquid oil feed thereby forming a suspension of the catalyst in the vapors. 1f desired, the feed may be vaporized prior to the admixture of regenerated catalyst therewith. Sufficient steam or other suitable gas to initially disperse the catalyst as discharged from feeder 19 is preferably introduced through line 20. Steam or other suitable gas may be supplied in greater quantities through line 20 when required to facilitate the vaporization of the combined oil charge and to supplement the vapors resulting from the vaporization of the feed stock and recycle oil to produce the required volume of gas to carry the catalyst through the conversion reactor 17. The dimension of reactor 17 may be varied and is such as to assure the desired conversion dependent upon variable conditions used such as the feed stock, catalyst and quantities thereof employed. Operating conditions in the conversion Zone such as the ratio by weight of the catalyst to fresh feed stock may be and preferably are `maintained as set forth in said co-pending application, Serial No. 274,670, now Patent No. 2,253,486, that is greater than 2.5 to l, and preferably greater than 5 to 1. The gaseous mixture of feed stock, catalyst and steam,

zgvs 12,398

. l K d ows. upwardly. through. reactor, 17. during which ow couversion or cracking of the oiLto the desired extent occurs.

Reaction products pass from thertop of reactor 17 to a separationLsystemtprovided: pursuant'to `theipresentrinventionwliichl is especially. iefectivef for: `the recoverylofecatalystfromithe.vaporous reaction products.

Asshown, this comprises ay settling` tank l21/` of: greater cross-sectional area inthe direction of flow thantne conversion zone'inwhich the major proportionsof-fthe suspended catalyst is ythus'separatedlbymimple settling,the separated catalyst `flowing bygravity from the vbottom of tank-21`t'hrough conduit 22 to `thetop ofa steamstripping tower -27 andthe vapors containinga relatively Lsmall fraction of tine catalytic material `are withdr'awnrat the top -through-r :line 124. These r vapors passv through: line24 tof a vsuitable separator such `as--cyclone type of `dust Vcollle'ctor25 wherein rnostv ofrthe remainingsuspended catalystis separatedby Vcentrifugal force due to the relative high velocity of the 'vapors in passing therethrough, and then pass to tower 27 by gravity iiow from they bottom ofthe separator'through line 26.

-Stripping tower -27 serves to displace 'hydrocarbon vapors contained in the voids between the particles of catalyst and issuitably provided with bafes 27a and 27 b to-e'tfectively expose the catalyst layer passing downwardly therethrough to the stripping or displacing-action of -a countercurrently owingcurrent of steam introduced atV the base of the tower through line 28. vSteam containing the oil vapors displaced from the catalyst is withdrawn from the top of the tower through line 29 and combined withthe vapor steam from -tank 21. Used catalyst falls from the bottom of tower 27 into a surge drum 30. Figure 2 is an enlarged View of tower 27 and illustrates the ow of catalyst downwardly therethrough, and Figure 3 isa sectional view taken along line 3-3.

The gas-solid separation zones constituted by settler 21 and cyclone ZS-are maintained at a temperatureabove the condensationV temperature of the vapors and serve to separate all but a small fraction of the total suspended solids, 'this unseparatedfractionl being normally less than 1% ofthe total and preferably of the order of 0.3% or less. The loss of this small percentage, however, would constitute a serious economical obstacle due to the exceedingly high quantities of catalyst circulated in catalytic systems of this type. In addition the consequent con tamination of the liquid products by its presence therein would be highly undesirable.

The pressure of the gas components at the inlets tothe conversion and regeneration zones obviously willA'necessarily be in excess of atmospheric pressure in both cases since a pressure drop is inevitable in the passage .of the gas component through the system. Catalyst particles must be introduced to these inlets from drums 18 and 30 against the back pressure thus exerted in these inlets. Either feederl) or 41, or both may bev solids-pump of th'eFuller-Kinyon type as previously proposedin Degnen Patent blo-2,205,569. Since cyclone25 discharges to Y tower 32 the pressure Amaintained therein must be suiliciently in'excess of atmospheric pressure yto overcornethe pressure drop in tower 32, and correspondingly higher than `the pressure in cyclone 49 fromwhich'discharge of tlue gas is to the atmosphere. -Asillustrated in'd'etaiI-:in Figure 2, avertically extending and downwardlyowing columnar mass of catalyst particles is maintained in tower '27 by the addition of used catalyst particles from settler 21 and cyclone 2S, and inert gas is introduced through'line 23 at a pressuresuicient to cause the gas to owupwardly in intimate contact with the down-owng mass. Thus the catalyst particles are discharged fromy the base of the columnar mass into a gaseous atmosphere havingapressure substantially higher than the'pressure prevailingat the top ofthe said mass, this increase corresponding to the pressure drop across the bai'liedportioniof tower-27.

between separator-2S and separator 49 isthus madeavail eliminated.

Preferably, the vaporous conversion products containing the small amount of residual catalyst ,are passed through line 31 to a cooling or partial condensationzone, suitably constituted by the lower section of a fractionating tower32. Fractionating tower 32 may be-abubbletower of conventional design adapted toiseparate the vaporous conversion products into liquid fractions of desired' boiling ranges, for example a low boiling fraction Aconsisting of hydrocarbons within the gasolineboilingrangemayfbe withdrawn overhead through line 33, a light gas; oihfrac- Y tion through the side draw-off line 34, and a heavy gas oil fraction through side draw-'od line 35. Condensate from vapors withdrawn through line 33 may be returnedto. the top tower as re'ux'in the conventional manner.VV

The lower section oi"tower"324 ispreferably provided with battles 36 or other suitable means forgpromo'ting gas-liquid contact. 'A portion of the heavy gas o`il cut withdrawn through line 35 is cooled and. returned tothe cooling section'in the Vlower part of tower 32 through line'37and passes downwardly over thebailies 36 in countercurrent ilow to 'the vapors introduced. throughline 31. The incoming vapors are thereby cooled suicien'tly tocondense a small fraction. of` the highest Aboiling constituents, for example about`l0% andhpreferably of the order of about 5 or less ofthe total incorningvapors; The' residual catalyst is entrairied and concentrated in'the high boiling fraction thus produced and withdrawn through line,39. This fraction is ,then preferably silbjected ,to further treatment ina catalytic conversion .Zone with additional quantities'of feed. It may. for example be suitably recycled to the same conversion zone in'which it was'initially producedbypurnp .40 and' line 'I4'a's previously described.

`In the regeneration flow, used catalyst is fedfrom drum 30 (in which'the upper surface of the catalyst mass'is indicated by dotted line62) by suitable meanssuch as screw feeder'41 to pipe 42 and iscarried thereinjbya current of voxygen-containingV gas such .as air injected through line' 43 to regenerationor.combustion chamber 44 in which combustion ofthe carbonaceous kdeposit on the spent catalyst' occurs 'during the passage ofthe catalyst therethrough., .Steam may be introduced to`line^42 if desired' through line 45.

Combustion gases bearing *thev regenerated. catalyst pass .f1-om. chamber 44.into a suitable recoveringjsystem'for separatingthe catalyst. As shown,"tliis system comprises va settlingtank'46`whereinmost of the` catalyst. is separated and flows downwardly therefrom through conduit "47 to 'surge drum 18. Theseparated gases containing a small residual amount ofcatalyst fines leave separator 46 Yat Ithe'top through line'48 andv pass to'a cyclone type ofdust collector 49, wherein. substantailly complete separation of they ,catalyst iseifected. The separated catalyst from 'collector 49"theirilowsdownwardly through line50 vand \'is'combined"with^the initially separatedl catalystin drum 1li-'from which-it isk fed directly to the conversion' stage; by feeder"19,"as previouslyfdescribed. "Drum 18' and feeder `19 maybe'suitablyiprovidedwith heat insulation'materi'al to obviate loss'of heat 4by the regenerated catalyst in'jits Apassage therethrough.

ItA isv to be understoodA thatthe` embodimentof'the `in-V vention desc'r'ibedincthe foregoingis illustrative only; and

that 4theessential features offthe invention are" capable of use inawide'vari'ety ofmodiedprocess ows. =All-such modifications are intended to be -included'within Vthe scope of the; appended" claim.

'I 'claimz A continuous process i for- `the" catalyticfconversioneof hydrocarbonswherein-v` saidv hydrocarbons are contacted in igaseouslform 4with powdered Asolidscatalyst; andi -v'vherein said powdered catalyst is continuously circulated within an enclosed system through a recation zone and aregeneration zone, which process includes the steps of: continuously introducing said hydrocarbons into the lower portion of said reaction zone and passing same upwardly to form a suspension of said powdered catalyst in uptlowing reactant gases; separating catalyst from reactant gases and continuously withdrawing a stream of reactant gases from which catalyst has been separated from said enclosed system; introducing said separated catalyst into the upper region of a vertically extended stripping zone and maintaining a ,continuously owing stream of said catalyst passing downwardly within said stripping zone; introducing a stream of stripping gas into the lower region of said stripping zone and owng said stripping gas coun tercurrently up through descending solids; discharging catalyst from the lower region of said stripping zone; feeding said withdrawn catalyst into a regenerating gas in said regeneration zone; regenerating said catalyst in said regeneration zone and reintroducing said regenerated catalyst into said reaction zone.

References Cited in the le of this patent UNITED STATES PATENTS 1,577,534 Miller Mar. 23, 1926 1,836,301 Bechthold Dec. 15, 1931 1,863,803 Patenburg .lune 21, 1932 2,079,158 De Rachat May 4, 1937 2,231,424 Huppke Feb. 11, 1941 2,273,075 Weems Feb. 17, 1942 2,302,209 Goddin Nov. 17, 1942 2,305,569 Degnen et al. Dec. 15, 1942 2,353,495 Payne July 11, 1944 2,403,375 Kassel July 2, 1946 

